JP2657600B2 - Emulsion adhesive excellent in initial adhesiveness and method for producing the same - Google Patents
Emulsion adhesive excellent in initial adhesiveness and method for producing the sameInfo
- Publication number
- JP2657600B2 JP2657600B2 JP4278112A JP27811292A JP2657600B2 JP 2657600 B2 JP2657600 B2 JP 2657600B2 JP 4278112 A JP4278112 A JP 4278112A JP 27811292 A JP27811292 A JP 27811292A JP 2657600 B2 JP2657600 B2 JP 2657600B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- vinyl acetate
- emulsion
- parts
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高固形分濃度であって
も低粘度であり、初期接着性、接着力、耐水強度の大で
ある初期接着性に優れた酢酸ビニル−エチレン共重合体
エマルジョン接着剤及びその製造方法に関するものであ
る。BACKGROUND OF THE INVENTION The present invention relates to a vinyl acetate-ethylene copolymer having a low viscosity even at a high solid content and having excellent initial adhesiveness, adhesive strength and water resistance. The present invention relates to an emulsion adhesive and a method for producing the same.
【０００２】[0002]
【従来の技術】接着剤に要求される性能は多種、多様で
あるが、近年合成樹脂エマルジョンを使用する接着及び
粘着分野においては、生産性向上のため高速接着機械が
導入され、エマルジョン塗布後の接着力の発現が速い、
いわゆる初期接着性の優れた接着剤が望まれたり、また
塗工時の乾燥エネルギーの節減のために、エマルジョン
に対しては固形分ができるだけ高く、かつ低粘度で安定
であり、更に各種基材への接着力等の性能が極めて高い
ものであることが要望されている。2. Description of the Related Art The performance required of adhesives is various and diverse. In recent years, in the field of adhesion and adhesion using synthetic resin emulsions, a high-speed bonding machine has been introduced to improve productivity. Fast expression of adhesive strength,
In order to reduce the drying energy during coating, it is desirable to have an adhesive with excellent initial adhesiveness. It is demanded that the performance, such as adhesive strength, is extremely high.
【０００３】かかる要望にこたえるものとして、高固形
分酢酸ビニル−エチレン共重合体エマルジョンが知られ
ている。[0003] To meet such demands, a high solid content vinyl acetate-ethylene copolymer emulsion is known.
【０００４】例えば、特開昭６３−２２３０５３号公報
には低分子量ポリビニルアルコールと界面活性剤の存在
のもとに重合した約６５乃至７０重量％の固形分の安定
な酢酸ビニル−エチレン共重合体エマルジョンが記載さ
れている。また特開平２−２７４７０７号公報には低分
子量ポリビニルアルコールと界面活性剤の存在のもとに
重合した６０〜７０重量％の固形分を有する酢酸ビニル
・エチレン・アクリル酸共重合体エマルジョンが記載さ
れている。更に、特開平２−２８９６４０号公報に低分
子量の部分けん化ポリビニルアルコールと界面活性剤を
含有した固形分が６５〜７０重量％の酢酸ビニル・エチ
レン共重合体エマルジョンが記載されている。For example, JP-A-63-223053 discloses a stable vinyl acetate-ethylene copolymer having a solid content of about 65 to 70% by weight, which is polymerized in the presence of a low molecular weight polyvinyl alcohol and a surfactant. An emulsion is described. JP-A-2-274707 discloses a vinyl acetate / ethylene / acrylic acid copolymer emulsion having a solid content of 60 to 70% by weight, which is polymerized in the presence of a low molecular weight polyvinyl alcohol and a surfactant. ing. Further, JP-A-2-289640 discloses a vinyl acetate / ethylene copolymer emulsion containing a low molecular weight partially saponified polyvinyl alcohol and a surfactant and having a solid content of 65 to 70% by weight.
【０００５】しかしながらこれらの提案された酢酸ビニ
ル−エチレン共重合体エマルジョンや酢酸ビニル・エチ
レン・アクリル酸共重合体エマルジョンには乳化分散剤
として界面活性剤を酢酸ビニル単位の１００重量部を基
準として通常２〜５重量部、少なくとも１重量部以上を
配合したものであり、この結果これらエマルジョンを接
着剤として使用したときに界面活性剤の影響により耐水
接着力の大幅な低下が避けられない。However, in these proposed vinyl acetate-ethylene copolymer emulsions and vinyl acetate-ethylene-acrylic acid copolymer emulsions, a surfactant is usually used as an emulsifying dispersant based on 100 parts by weight of vinyl acetate units. 2 to 5 parts by weight, at least 1 part by weight or more, as a result, when these emulsions are used as an adhesive, a significant decrease in the water-resistant adhesive strength cannot be avoided due to the effect of the surfactant.
【０００６】また従来の酢酸ビニル−エチレン共重合体
エマルジョンの製法により固形分が６５〜７５重量％の
ごとき高固形分にすると、粘度が１０，０００ｃｐｓ以
上の高粘度となり、重合中除熱がしにくくなり製造が難
しくなる。Further, when the solid content is increased to a high solid content of 65 to 75% by weight according to a conventional method for producing a vinyl acetate-ethylene copolymer emulsion, the viscosity becomes as high as 10,000 cps or more, and heat is removed during polymerization. And manufacturing becomes difficult.
【０００７】高固形分低粘度のエマルジョンは粒子径を
大きくすると得られる。即ち粘度を低下させるには平均
粒子径０．６〜１．２μｍが良い。ポリビニルアルコー
ルを保護コロイドとして使用すると、粒子径が大きいた
めエマルジョンの放置安定性が悪くなる傾向がある。こ
の放置安定性を改善するために、保護コロイドとしての
ポリビニルアルコールと共に界面活性剤を酢酸ビニル単
位１００重量部あたり１重量部以上併用することが通常
である。[0007] An emulsion having a high solid content and a low viscosity can be obtained by increasing the particle size. That is, in order to reduce the viscosity, the average particle diameter is preferably 0.6 to 1.2 μm. When polyvinyl alcohol is used as a protective colloid, the emulsion tends to have poor storage stability due to its large particle size. In order to improve the storage stability, a surfactant is usually used together with polyvinyl alcohol as a protective colloid in an amount of 1 part by weight or more per 100 parts by weight of vinyl acetate unit.
【０００８】また粘度の低下をはかるために、ポリビニ
ルアルコールの分子量を低下させるなどの工夫がなされ
てきたが、それでも界面活性剤の添加量は酢酸ビニル単
位１００重量部を基準として１重量部以下とすることが
できなかった。In order to reduce the viscosity, various measures have been taken, such as reducing the molecular weight of polyvinyl alcohol. However, the amount of the surfactant to be added is 1 part by weight or less based on 100 parts by weight of vinyl acetate units. I couldn't.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、エマルジョ
ンを被着体に塗工乾燥し、接着剤として使用する場合に
エマルジョンの安定化のために使用されている界面活性
剤が耐水接着力を阻害することに注目し、安定性の良い
高固形分濃度の酢酸ビニル−エチレン共重合体エマルジ
ョンからなる初期接着性に優れたエマルジョン接着剤で
あって、界面活性剤を全く使用しないか、あるいは使用
するとしても極めて少量の使用で安定性が確保でき、被
着体への耐水接着力を向上させると共に塗工後の接着力
の発現の速い、いわゆる初期接着性に優れた酢酸ビニル
−エチレン共重合体エマルジョンを得ることを目的とし
ている。According to the present invention, a surfactant used for stabilizing an emulsion when the emulsion is applied to an adherend and used as an adhesive has a water-resistant adhesive strength. It is an emulsion adhesive with excellent initial adhesion consisting of a vinyl acetate-ethylene copolymer emulsion with a high solid content and good stability, noting that no surfactant is used. Even so, the use of a very small amount can ensure stability, improve the water-resistant adhesion to the adherend, and exhibit high adhesion after coating. The aim is to obtain a coalesced emulsion.
【００１０】[0010]
【課題を解決するための手段】本発明は、 （１）酢酸ビニル−エチレン共重合体エマルジョンにお
いて、該共重合体中の酢酸ビニル単位１００重量部あた
りスルホン酸基含有変性ポリビニルアルコール系樹脂
０．５〜１０重量部を含み、固形分が６５〜７５重量
％、粘度が１０，０００ｃｐｓ以下、平均粒子径が０．
６〜１．２μｍであって、前記共重合体の組成が酢酸ビ
ニル９５〜６０重量％、エチレン５〜４０重量％からな
る初期接着性に優れたエマルジョン接着剤、 （２）乳化分散剤として酢酸ビニル−エチレン共重合体
中の酢酸ビニル単位１００重量部あたり１重量部を越え
ないポリオキシエチレン系非イオン界面活性剤を含有す
る（１）記載の初期接着性に優れたエマルジョン接着
剤、 （３）酢酸ビニル、該酢酸ビニル１００重量部あたりス
ルホン酸基含有変性ポリビニルアルコール系樹脂０．５
〜１０重量部および適量の水を混合して、モノマー乳化
液とし、エチレン分圧５〜１５０Ｋｇ／ｃｍ2 、反応温
度１０〜１５０℃において、ラジカル重合開始剤または
レドックス系触媒を用いてエマルジョン重合を行い、固
形分６５〜７５重量％、粘度１０，０００ｃｐｓ以下、
平均粒子径０．６〜１．２μｍの組成として酢酸ビニル
含有量９５〜６０重量％、エチレン含有量５〜４０重量
％である初期接着性に優れたエマルジョン接着剤の製造
方法、及び （４）乳化分散剤として酢酸ビニル−エチレン共重合体
中の酢酸ビニル単位１００重量部あたり１重量部を越え
ないポリオキシエチレン系非イオン界面活性剤を含有す
る（３）記載の初期接着性に優れたエマルジョン接着剤
の製造方法を開発することにより上記の目的を達成し
た。According to the present invention, there is provided (1) a vinyl acetate-ethylene copolymer emulsion containing a sulfonic acid group-containing modified polyvinyl alcohol-based resin per 100 parts by weight of vinyl acetate units in the copolymer. It contains 5 to 10 parts by weight, has a solid content of 65 to 75% by weight, a viscosity of 10,000 cps or less, and has an average particle size of 0.
An emulsion adhesive having an initial adhesion of 6 to 1.2 μm and having a copolymer composition of 95 to 60% by weight of vinyl acetate and 5 to 40% by weight of ethylene; (2) acetic acid as an emulsifying dispersant; (1) The emulsion adhesive having excellent initial adhesiveness according to (1), containing no more than 1 part by weight of a polyoxyethylene-based nonionic surfactant per 100 parts by weight of vinyl acetate units in the vinyl-ethylene copolymer. ) Vinyl acetate, 0.5 parts by weight of a modified sulfonic acid group-containing modified polyvinyl alcohol resin per 100 parts by weight of the vinyl acetate
10 to 10 parts by weight and an appropriate amount of water are mixed to form a monomer emulsion, and emulsion polymerization is performed using a radical polymerization initiator or a redox catalyst at an ethylene partial pressure of 5 to 150 kg / cm 2 and a reaction temperature of 10 to 150 ° C. Done, solid content 65-75% by weight, viscosity 10,000 cps or less,
(4) a method for producing an emulsion adhesive having excellent initial adhesion, having a vinyl acetate content of 95 to 60% by weight and an ethylene content of 5 to 40% by weight as a composition having an average particle diameter of 0.6 to 1.2 μm; (3) The emulsion excellent in initial adhesiveness according to (3), containing a polyoxyethylene-based nonionic surfactant not exceeding 1 part by weight per 100 parts by weight of vinyl acetate units in a vinyl acetate-ethylene copolymer as an emulsifying dispersant. The above object has been achieved by developing a method for producing an adhesive.
【００１１】本発明の酢酸ビニル−エチレン共重合体の
原料は主たるモノマーとして酢酸ビニル及びエチレンが
ある。これ以外に第三のコモノマーとして酢酸ビニル以
外のビニルエステル類、例えばプロピオン酸ビニル、酪
酸ビニル、吉草酸ビニル、カプロン酸ビニル、ヘプタン
酸ビニル、カプリル酸ビニル、ペラルゴン酸ビニル、バ
ーサチック酸ビニル、ｎ−ウンデカン酸ビニル及びラウ
リル酸ビニル等、アクリル酸エステル類、例えばアクリ
ル酸メチル、アクリル酸エチル、及びアクリル酸−２−
エチルヘキシル等、アクリルアミド、アクリルアミド誘
導体、例えばアルコキシメチルアクリルアミド及びＮ−
メチロールアクリルアミド等及びメタクリル酸エステル
類、例えばメタクリル酸メチル、メタクリル酸エチル、
メタクリル酸ブチル、メタクリル酸−２−エチルヘキシ
ルなどの共重合可能なモノマーを共重合させても良い。
これら第三のコモノマーは、酢酸ビニル１００重量部に
対して１０重量部以下であることが好ましい。The raw materials of the vinyl acetate-ethylene copolymer of the present invention include vinyl acetate and ethylene as main monomers. In addition, vinyl esters other than vinyl acetate as the third comonomer, such as vinyl propionate, vinyl butyrate, vinyl valerate, vinyl caproate, vinyl heptanoate, vinyl caprylate, vinyl pelargonate, vinyl versatate, n- Acrylic esters such as vinyl undecanoate and vinyl laurate, such as methyl acrylate, ethyl acrylate, and acrylic acid-2-
Acrylamide, acrylamide derivatives such as ethylhexyl and the like, for example, alkoxymethylacrylamide and N-
Methylol acrylamide and the like and methacrylates, such as methyl methacrylate, ethyl methacrylate,
A copolymerizable monomer such as butyl methacrylate or 2-ethylhexyl methacrylate may be copolymerized.
It is preferable that these third comonomers are 10 parts by weight or less based on 100 parts by weight of vinyl acetate.
【００１２】本発明の保護コロイドとしてはスルホン酸
基含有変性ポリビニルアルコール系樹脂である。このも
のはエマルジョンの保護コロイドとして有用なものであ
り、市販品（日本合成化学工業株式会社、商品名：ゴー
セランＬ−３２６６，アニオンタイプ、けん化度８６〜
９０％のポリビニルアルコール変性物）もある。The protective colloid of the present invention is a modified polyvinyl alcohol resin containing a sulfonic acid group. This is useful as a protective colloid of the emulsion, and is a commercially available product (Nippon Synthetic Chemical Industry Co., Ltd., trade name: Goselan L-3266, anion type, saponification degree 86-
90% modified polyvinyl alcohol).
【００１３】このスルホン酸基含有変性ポリビニルアル
コール系樹脂は、使用酢酸ビニル単位１００重量部あた
り０．５〜１０重量部、好ましくは１〜６重量部を使用
する。この量が０．５重量部未満の場合には粗粒が生
じ、エマルジョンとしての安定性を阻害し、沈殿物を生
じ易い。一方、１０重量部を越えて使用したエマルジョ
ンはそれから作られたフィルムの耐水性が悪く、水中で
その一部が溶解するようになるなど本発明の目的に沿わ
ないエマルジョンとなる。The sulfonic acid group-containing modified polyvinyl alcohol resin is used in an amount of 0.5 to 10 parts by weight, preferably 1 to 6 parts by weight, per 100 parts by weight of the vinyl acetate unit used. If this amount is less than 0.5 parts by weight, coarse particles are formed, which hinders the stability of the emulsion and easily forms a precipitate. On the other hand, an emulsion used in excess of 10 parts by weight is not suitable for the purpose of the present invention, for example, the film made therefrom has poor water resistance, and a part of the emulsion is dissolved in water.
【００１４】またこの保護コロイドの使用は上記の範囲
内で共重合されたエマルジョンの平均粒子径が０．６〜
１．２μｍに納まり、比較的大きな粒子径を示し、粘度
も１０，０００ｃｐｓ以下になる。The use of this protective colloid is effective when the average particle size of the emulsion copolymerized within the above range is 0.6 to 0.6.
It falls within 1.2 μm, exhibits a relatively large particle size, and has a viscosity of 10,000 cps or less.
【００１５】更に本発明において、分散剤として通常の
ポリビニルアルコールを併用しても良い。この場合好ま
しくは、エマルジョン粘度の温度依存性の少ない部分け
ん化ポリビニルアルコールが良い。ポリビニルアルコー
ルの使用量は、酢酸ビニル１００重量部あたり３重量部
以下が好ましい。３重量部より多い使用量では、エマル
ジョンの粘度が１０，０００ｃｐｓを超えて製造が困難
となる。Further, in the present invention, ordinary polyvinyl alcohol may be used in combination as a dispersant. In this case, a partially saponified polyvinyl alcohol having less temperature dependence of the emulsion viscosity is preferable. The amount of polyvinyl alcohol used is preferably 3 parts by weight or less per 100 parts by weight of vinyl acetate. If the amount is more than 3 parts by weight, the viscosity of the emulsion exceeds 10,000 cps, and the production becomes difficult.
【００１６】保護コロイドとして、スルホン酸基含有変
性ポリビニルアルコール系樹脂を使用するときは、通常
単独処方（界面活性剤を併用しない）で安定性の良い高
固形分エマルジョンが得られるが、何らかの都合、例え
ば乳化作用の強化、被接着物との親和性の改善などの目
的でポリオキシエチレン系非イオン界面活性剤を併用す
ることも可能である。この場合には酢酸ビニル１００重
量部を基準として１重量部未満、好ましくは０．８重量
部以下の添加に止めるべきである。１重量部をこえる添
加では接着剤として使用するとき、被着体への阻害物質
となり、接着力が小さくなる原因、特に耐水接着力低下
の原因となり易い。この範囲内の添加であればエマルジ
ョンの平均粒子径にも悪影響はなく、粘度も１０，００
０ｃｐｓ以下の低粘度で安定なエマルジョンが得られ
る。When a modified sulfonic acid group-containing polyvinyl alcohol-based resin is used as a protective colloid, a stable high solid content emulsion can be obtained usually by a single formulation (without using a surfactant). For example, a polyoxyethylene-based nonionic surfactant can be used in combination for the purpose of enhancing the emulsifying action and improving the affinity with the adherend. In this case, the addition should be limited to less than 1 part by weight, preferably 0.8 part by weight or less based on 100 parts by weight of vinyl acetate. When added as more than 1 part by weight, when used as an adhesive, it becomes an inhibitory substance to an adherend and tends to cause a decrease in adhesive strength, particularly a decrease in water-resistant adhesive strength. If added in this range, there is no adverse effect on the average particle size of the emulsion and the viscosity is also 10,000.
A stable emulsion having a low viscosity of 0 cps or less can be obtained.
【００１７】この場合、用いることのできるポリオキシ
エチレン系非イオン界面活性剤の具体例としては、ポリ
オキシエチレンアルキルエーテル、ポリオキシエチレン
アルキルアリルエーテル、ポリオキシエチレン脂肪酸エ
ステル、ポリオキシエチレンソルビタン脂肪酸エステル
等があげられる。In this case, specific examples of the polyoxyethylene-based nonionic surfactant that can be used include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. And the like.
【００１８】本発明に用いるラジカル重合開始剤には、
過硫酸アンモニウム、過硫酸カリウム及び過硫酸ナトリ
ウムのような過硫酸塩化合物、過酸化水素、ｔ−ブチル
ハイドロパーオキサイド、クメンハイドロパーオキサイ
ド、ジイソプロピルベンゼンハイドロパーオキサイド、
過酸化ベンゾイルのような過酸化物及びペルオキソホウ
酸アンモニウム、ペルオキソホウ酸カリウム、及びペル
オキソホウ酸ナトリウムのようなペルオキソホウ酸塩な
どがあり、場合によってはこれに還元剤を併用したいわ
ゆるレドックス触媒が含まれるが、水溶性のラジカル重
合開始剤が操作上便利である。使用量は反応系の総重量
に対して０．０１〜１０重量％で、特に０．０５〜５重
量％が好ましい。The radical polymerization initiator used in the present invention includes:
Ammonium persulfate, persulfate compounds such as potassium persulfate and sodium persulfate, hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide,
There are peroxides such as benzoyl peroxide and ammonium peroxoborate, potassium peroxoborate, and peroxoborates such as sodium peroxoborate. Although included, water-soluble radical polymerization initiators are convenient for operation. The amount used is 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total weight of the reaction system.
【００１９】本発明の酢酸ビニル−エチレン共重合体エ
マルジョンの工業的生産においては、高圧反応器を用い
バッチ式、反連続式、連続式の何れかの方法であり、採
算性のある除熱可能量であるためには、エマルジョン粘
度が１０，０００ｃｐｓ以下である必要がある。酢酸ビ
ニル−エチレン共重合体のエチレン含量は重合過程のエ
チレン圧に依存し、エチレン圧が高いほどエチレン含量
は多くなる。エチレン含量は主に該エマルジョンから作
られたフィルムの強伸度などのフィルム性質に影響し、
それはまた被着体に対する接着性に影響する。従って多
岐にわたる要求に応じるにはさまざまなエチレン圧の下
で、製造されなければならないので通常その範囲は５〜
１５０ｋｇ／ｃｍ2 と考えられるが、１０〜１００ｋｇ
／ｃｍ2が最も一般的である。In the industrial production of the vinyl acetate-ethylene copolymer emulsion of the present invention, any one of a batch type, a non-continuous type, and a continuous type using a high-pressure reactor is used, and it is profitable to remove heat. In order to be an amount, the emulsion viscosity needs to be 10,000 cps or less. The ethylene content of the vinyl acetate-ethylene copolymer depends on the ethylene pressure in the polymerization process, and the higher the ethylene pressure, the higher the ethylene content. Ethylene content mainly affects film properties such as high elongation of films made from the emulsion,
It also affects the adhesion to the adherend. Therefore, in order to meet a wide variety of requirements, it must be manufactured under various ethylene pressures, so that the range is usually 5 to 5.
150 kg / cm 2 , but 10-100 kg
/ Cm 2 is most common.
【００２０】反応温度は１０〜１５０℃で特に３０〜１
００℃が好ましい。The reaction temperature is from 10 to 150 ° C., especially from 30 to 1
00 ° C is preferred.
【００２１】乳化重合は、所定量の酢酸ビニル、スルホ
ン酸基含有変性ポリビニルアルコール系樹脂、必要に応
じてポリオキシエチレン系非イオン界面活性剤及び水を
混合して酢酸ビニル乳化液とし、これにエチレンを加圧
し行われる。In the emulsion polymerization, a predetermined amount of vinyl acetate, a sulfonic acid group-containing modified polyvinyl alcohol-based resin, a polyoxyethylene-based nonionic surfactant and, if necessary, water are mixed to form a vinyl acetate emulsion. This is performed by pressurizing ethylene.
【００２２】このように製造された酢酸ビニル−エチレ
ン共重合体エマルジョンは、スルホン酸基含有変性ポリ
ビニルアルコール系樹脂が酢酸ビニル単位１００重量部
あたり０．５〜１０重量部であり、固形分６５〜７５重
量％、粘度１０，０００ｃｐｓ以下、平均粒径が０．６
〜１．２μｍであり、酢酸ビニル９５〜６０重量％、エ
チレン５〜４０重量％からなる共重合体エマルジョンと
することができる。なお、ポリオキシエチレン系非イオ
ン界面活性剤を併用した場合は、この界面活性剤は酢酸
ビニル単位１００重量部あたり１重量部未満である。In the vinyl acetate-ethylene copolymer emulsion thus produced, the sulfonic acid group-containing modified polyvinyl alcohol-based resin is 0.5 to 10 parts by weight per 100 parts by weight of vinyl acetate unit, and has a solid content of 65 to 65 parts by weight. 75% by weight, viscosity of 10,000 cps or less, average particle size of 0.6
.About.1.2 .mu.m, and a copolymer emulsion composed of 95-60% by weight of vinyl acetate and 5-40% by weight of ethylene can be obtained. When a polyoxyethylene-based nonionic surfactant is used in combination, the amount of this surfactant is less than 1 part by weight per 100 parts by weight of vinyl acetate units.
【００２３】このエマルジョンは高固形分濃度であって
も低粘度であり、このため除熱が容易で製造に困難はな
く、また平均粒子径が適当であるため低粘度が維持でき
るだけでなく、安定性に優れている。最大の特徴は界面
活性剤を全く用いないか、用いるとしても従来法の約１
／３以下のごとき極めて少量の添加で済むため、接着強
度、特に耐水強度を高く維持できる特徴がもたらされ
た。This emulsion has a low viscosity even at a high solid content, so that heat removal is easy and there is no difficulty in production. In addition, since the average particle size is appropriate, low viscosity can be maintained and stable. Excellent in nature. The greatest feature is that no surfactant is used or even if it is used, it is about 1
Since only a very small amount, such as / 3 or less, can be added, the characteristic that the adhesive strength, especially the water resistance strength, can be kept high is provided.
【００２４】[0024]
【実施例】以下に本発明について実施例をもって具体的
に説明するが、本発明はこれらに限定されるものではな
い。エマルジョンの物性評価方法は、以下のとおりであ
る。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The method for evaluating the physical properties of the emulsion is as follows.
【００２５】（１）エマルジョン物性 固形分：１１０℃、３時間乾燥後の蒸発残分（重量
％） 粘度：ＢＬ型粘度計、１０ｒｐｍ、３０℃ 平均粒子径：水で固形分０．０１重量％に希釈調整
したエマルジョンを、レーザーを光源として動的光散乱
測定法により求めた。(1) Emulsion physical properties Solid content: 110 ° C., evaporation residue after drying for 3 hours (% by weight) Viscosity: BL viscometer, 10 rpm, 30 ° C. Average particle size: 0.01% by weight of solid content in water The emulsion adjusted to a pH of 1 was determined by dynamic light scattering measurement using a laser as a light source.
【００２６】（２）接着性能 初期接着性：Ｂライナー紙（坪量３００ｇ／ｍ2 ）
の表面に接着剤アプリケーターで３０ｇ／ｍ2 の割合に
塗布し、直ちにＢライナー紙の裏と貼りあわせ、ゴムロ
ールで３回押さえた後、５０％紙破に要する秒数を求
め、これを初期接着速度とした。 塩ビ・合板接着強度：合板にエマルジョンを１２ｇ
／９００ｃｍ2 塗布し、塩化ビニルシートを貼りあわ
せ、２Ｋｇ／ｃｍ2 で２４時間圧締後、２０℃、６５Ｒ
Ｈ％で２日間養生した。(2) Adhesion performance Initial adhesion: B liner paper (basis weight 300 g / m 2 )
Apply 30 g / m 2 on the surface of the sheet with an adhesive applicator, immediately adhere to the back of the B liner paper, press three times with a rubber roll, determine the number of seconds required for 50% paper break, and apply this to the initial bonding Speed. PVC / plywood adhesive strength: 12 g of emulsion on plywood
/ 900 cm 2, apply a vinyl chloride sheet, and press-clamp at 2 kg / cm 2 for 24 hours.
Cured at H% for 2 days.
【００２７】常態強度は、該積層板を１インチ幅に細断
し、２０℃、６５ＲＨ％、引張速度１０ｍｍ／ｍｉｎの
条件で１８０度剥離強度を測定した。また耐水強度は常
態強度と同一のサンプルを２０℃、水中２４時間浸漬
し、取り出し直後のサンプルを同一の条件で剥離強度を
測定した。The normal strength was measured by measuring the 180 ° peel strength under conditions of 20 ° C., 65 RH%, and a pulling speed of 10 mm / min by shredding the laminate to a width of 1 inch. The sample having the same water resistance as the normal strength was immersed in water at 20 ° C. for 24 hours, and the sample immediately after being taken out was measured for the peel strength under the same conditions.
【００２８】（実施例１）内容積６０Ｌのいかり型撹拌
機を備えたステンレス製溶解釜に以下の各成分を仕込
み、５０℃で２時間撹拌溶解し、均一な水溶液とした。 水 ７３６１．０ｇ ゴーセランＬ−３２６６＊ ７５０．０ｇ ＊ スルホン酸基含有変性ポリビニルアルコール系樹脂
（日本合成化学工業（株）製） 次に、該水溶液に第２リン酸ソーダ１４．３ｇ、メタ重
亜硫酸ソーダ２００ｇ添加溶解し、３０℃以下に冷却し
た。更に上記水溶液に酢酸ビニル１５５９３．８ｇを撹
拌しながら徐々に添加し、酢酸ビニルモノマーの乳化液
を得た。Example 1 The following components were charged into a stainless steel dissolving vessel equipped with a 60-liter internal stirrer and stirred and dissolved at 50 ° C. for 2 hours to obtain a uniform aqueous solution. Water 7361.0 g Gohselan L-3266 * 750.0 g * Sulfonic acid group-containing modified polyvinyl alcohol-based resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 200 g of soda was added and dissolved, and cooled to 30 ° C. or lower. Further, 15593.8 g of vinyl acetate was gradually added to the aqueous solution with stirring to obtain an emulsion of a vinyl acetate monomer.
【００２９】このモノマー乳化液の２５％を、内容積３
０Ｌのいかり型撹拌機を備えたステンレス製オートクレ
ーブに仕込み、続いてオートクレーブ内の空気を窒素及
びエチレンで充分置換した後撹拌下、モノマー乳化液を
７２℃に昇温すると共にエチレン圧を５０Ｋｇ／ｃｍ2
に昇圧した後、温度を７２℃、エチレン圧を５０Ｋｇ／
ｃｍ2 にコントロールしながら１時間重合した。この条
件を１時間維持した後モノマー乳化液の残りの７５％を
７時間にわたって均一に添加し重合を行った。またこの
際重合触媒として５．８％水溶液の過硫酸アンモニウム
１０８１ｇを重合の最初より１０時間にわたって、均一
に滴下した。なお９時間目より熟成温度を８０℃に昇温
し、１時間熟成を行った。25% of this monomer emulsion is filled with an internal volume of 3%.
A 0 L stainless steel autoclave equipped with a squeezing type stirrer was charged, followed by sufficiently replacing the air in the autoclave with nitrogen and ethylene, and then, while stirring, the monomer emulsion was heated to 72 ° C. and the ethylene pressure was reduced to 50 kg / cm. Two
After raising the pressure to 72 ° C, the ethylene pressure was increased to 50 kg /
The polymerization was carried out for 1 hour while controlling to 2 cm 2 . After maintaining this condition for 1 hour, the remaining 75% of the monomer emulsion was added uniformly over 7 hours to carry out polymerization. At this time, as a polymerization catalyst, 1081 g of a 5.8% aqueous solution of ammonium persulfate was dropped uniformly over 10 hours from the beginning of the polymerization. From the 9th hour, the aging temperature was raised to 80 ° C., and aging was performed for 1 hour.
【００３０】（実施例２）実施例１と同じ溶解釜に同方
法で下記の成分の均一な水溶液を得た。 水 ７３６１．０ｇ ゴーセランＬ−３２６６ ２５０．０ｇ ゴーセノールＧＬ−０３＊ ３７５．０ｇ ＊ ポリビニルアルコール（日本合成化学工業（株）
製） 次に実施例１の場合と同様に第２リン酸ソーダ、メタ重
亜硫酸ソーダおよび酢酸ビニルを加え、酢酸ビニルモノ
マー乳化液を得た後、実施例１と同方法にて重合を行っ
た。Example 2 A uniform aqueous solution of the following components was obtained in the same dissolving vessel as in Example 1 by the same method. Water 7361.0 g Gohselan L-3266 250.0 g Gohsenol GL-03 * 375.0 g * Polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd.)
Next, sodium biphosphate, sodium metabisulfite, and vinyl acetate were added in the same manner as in Example 1 to obtain a vinyl acetate monomer emulsion, and polymerization was performed in the same manner as in Example 1. .
【００３１】（実施例３）実施例１と同じ溶解釜に同方
法で下記の成分の均一な水溶液を得た。 水 ７３６１．０ｇ ゴーセランＬ−３２６６ ３７５．０ｇ ゴーセノールＧＬ−０３ ３７５．０ｇ エマルゲン９５０＊ ６２．５ｇ ＊ ポリオキシエチレン系非イオン界面活性剤（花王石
鹸（株）製） 次に実施例１の場合と同様に第２リン酸ソーダ、メタ重
亜硫酸ソーダ及び酢酸ビニルを加え酢酸ビニルモノマー
乳化液を得た後、実施例１と同方法にて重合を行った。Example 3 A uniform aqueous solution of the following components was obtained in the same dissolving vessel as in Example 1 by the same method. Water 7361.0 g Gohselan L-3266 375.0 g Gohsenol GL-03 375.0 g Emulgen 950 * 62.5 g * Polyoxyethylene nonionic surfactant (manufactured by Kao Soap Co., Ltd.) Similarly, a second sodium phosphate, sodium metabisulfite and vinyl acetate were added to obtain a vinyl acetate monomer emulsion, and polymerization was carried out in the same manner as in Example 1.
【００３２】（実施例４）スルホン酸基含有変性ポリビ
ニルアルコール系樹脂（ゴーセランＬ−３２６６）を１
０００ｇに増加した以外は実施例１と同様に重合を実施
した。Example 4 A modified polyvinyl alcohol resin containing a sulfonic acid group (Gohselan L-3266)
Polymerization was carried out in the same manner as in Example 1 except that the amount was increased to 000 g.
【００３３】（実施例５）エチレン圧を６０Ｋｇ／ｃｍ
2 とした以外は実施例１と同様に重合を実施した。Example 5 The ethylene pressure was increased to 60 kg / cm.
Except for using 2 was carried out similarly polymerized as in Example 1.
【００３４】（比較例１）実施例１と同じ溶解釜に同方
法で下記の成分の均一な水溶液を得た。 水 ７３６１．０ｇ ゴーセランＬ−３２６６ １８７１．０ｇ 該水溶液を使用した以外は実施例１と同一の方法にて重
合を行った。(Comparative Example 1) A homogeneous aqueous solution of the following components was obtained in the same dissolving vessel as in Example 1 by the same method. Water 7361.0 g Gohselan L-3266 1871.0 g Polymerization was carried out in the same manner as in Example 1 except that the aqueous solution was used.
【００３５】（比較例２）実施例１と同じ溶解釜に同方
法で下記の成分の均一な水溶液を得た。 水 ７３６１．０ｇ ゴーセノールＧＭ−１４＊ ６２５．０ｇ ＊ ポリビニルアルコール（日本合成化学工業（株）
製） エマルゲン９５０ ３７５．０ｇ 該水溶液を使用した以外は実施例１と同一の方法にて重
合を行った。Comparative Example 2 A uniform aqueous solution of the following components was obtained in the same dissolving vessel as in Example 1 by the same method. Water 7361.0 g Gohsenol GM-14 * 625.0 g * Polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd.)
375.0 g of Emulgen 950 Polymerization was carried out in the same manner as in Example 1 except that the aqueous solution was used.
【００３６】（比較例３）実施例１と同じ溶解釜に同方
法で下記の成分の均一な水溶液を得た。 水 ７３６１．０ｇ ゴーセランＬ−３２６６ ７５０．０ｇ エマルゲン９５０ ３７５．０ｇ 該水溶液を使用した以外は実施例１と同一の方法にて重
合を行った。Comparative Example 3 A uniform aqueous solution of the following components was obtained in the same dissolving vessel as in Example 1 by the same method. Water 7361.0 g Gohselan L-3266 750.0 g Emulgen 950 375.0 g Polymerization was carried out in the same manner as in Example 1 except that the aqueous solution was used.
【００３７】（比較例４）実施例１と同じ溶解釜に同方
法で下記の成分の均一な水溶液を得た。 水 ７３６１．０ｇ ゴーセランＬ−３２６６ ２５０．０ｇ ゴーセノールＧＬ−０３ ３７５．０ｇ エマルゲン９５０ ３７５．０ｇ 該水溶液を使用した以外は実施例１と同一の方法にて重
合を行った。以上の実施例及び比較例により製造した酢
酸ビニル−エチレン共重合体エマルジョンの諸物性と接
着性能結果を表１に示す。Comparative Example 4 A uniform aqueous solution of the following components was obtained in the same dissolving vessel as in Example 1 by the same method. Water 7361.0 g Gohselan L-3266 250.0 g Gohsenol GL-03 375.0 g Emulgen 950 375.0 g Polymerization was carried out in the same manner as in Example 1 except that the aqueous solution was used. Table 1 shows the physical properties and adhesion performance results of the vinyl acetate-ethylene copolymer emulsions produced by the above Examples and Comparative Examples.
【００３８】[0038]
【表１】 [Table 1]
【００３９】[0039]
【発明の効果】本発明によって得られた酢酸ビニル−エ
チレン共重合体系初期接着性に優れたエマルジョン接着
剤は、界面活性剤を用いなくとも安定性があり、また高
固形分濃度であっても低粘度であり、特に極めて初期接
着性に優れ、かつ該エマルジョンより得られたフィルム
は界面活性剤を含まないか、含んでも極めて少ないため
耐水強度が高く、強靭であり、更に柔軟性に富む特徴を
有しているため、種々接着剤に好適である。The emulsion adhesive obtained by the present invention, which is excellent in vinyl acetate-ethylene copolymer initial adhesiveness, is stable without using a surfactant, and has a high solid content even if it has a high solid content. Low viscosity, especially excellent initial adhesion, and the film obtained from the emulsion contains no or very few surfactants, so it has high water resistance, toughness, and more flexibility. Therefore, it is suitable for various adhesives.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 (Ｃ０９Ｊ 131/04 129:04） Continued on the front page (51) Int.Cl. 6 Identification number Reference number in the agency FI Technical indication (C09J 131/04 129: 04)
Claims (4)
ョンにおいて、該共重合体中の酢酸ビニル単位１００重
量部あたりスルホン酸基含有変性ポリビニルアルコール
系樹脂０．５〜１０重量部を含み、固形分が６５〜７５
重量％、粘度が１０，０００ｃｐｓ以下、平均粒子径が
０．６〜１．２μｍであって、前記共重合体の組成が酢
酸ビニル９５〜６０重量％、エチレン５〜４０重量％か
らなることを特徴とする初期接着性に優れたエマルジョ
ン接着剤。1. A vinyl acetate-ethylene copolymer emulsion containing 0.5 to 10 parts by weight of a sulfonic acid group-containing modified polyvinyl alcohol-based resin per 100 parts by weight of vinyl acetate units in the copolymer, and having a solid content of 65-75
% By weight, a viscosity of 10,000 cps or less, an average particle diameter of 0.6 to 1.2 μm, and a composition of the copolymer comprising 95 to 60% by weight of vinyl acetate and 5 to 40% by weight of ethylene. Emulsion adhesive with excellent initial adhesion.
共重合体中の酢酸ビニル単位１００重量部あたり１重量
部を越えないポリオキシエチレン系非イオン界面活性剤
を含有する請求項１記載の初期接着性に優れたエマルジ
ョン接着剤。2. The initial adhesion according to claim 1, wherein the emulsifying dispersant contains not more than 1 part by weight of a polyoxyethylene-based nonionic surfactant per 100 parts by weight of vinyl acetate units in the vinyl acetate-ethylene copolymer. Emulsion adhesive with excellent properties.
あたりスルホン酸基含有変性ポリビニルアルコール系樹
脂０．５〜１０重量部および適量の水を混合して、モノ
マー乳化液とし、エチレン分圧５〜１５０Ｋｇ／ｃｍ
2 、反応温度１０〜１５０℃において、ラジカル重合開
始剤またはレドックス系触媒を用いてエマルジョン重合
を行い、固形分６５〜７５重量％、粘度１０，０００ｃ
ｐｓ以下、平均粒子径０．６〜１．２μｍの組成として
酢酸ビニル含有量９５〜６０重量％、エチレン含有量５
〜４０重量％である初期接着性に優れたエマルジョン接
着剤の製造方法。3. A monomer emulsion by mixing vinyl acetate, 0.5 to 10 parts by weight of a sulfonic acid group-containing modified polyvinyl alcohol-based resin per 100 parts by weight of the vinyl acetate, and an appropriate amount of water. 150Kg / cm
2. Emulsion polymerization is performed at a reaction temperature of 10 to 150 ° C. using a radical polymerization initiator or a redox catalyst to obtain a solid content of 65 to 75% by weight and a viscosity of 10,000 c.
ps or less, a composition having an average particle diameter of 0.6 to 1.2 μm, a vinyl acetate content of 95 to 60% by weight, and an ethylene content of 5
A method for producing an emulsion adhesive having excellent initial adhesiveness of 40% by weight.
共重合体中の酢酸ビニル単位１００重量部あたり１重量
部を越えないポリオキシエチレン系非イオン界面活性剤
を含有する請求項３記載の初期接着性に優れたエマルジ
ョン接着剤の製造方法。4. The initial adhesion according to claim 3, wherein the emulsifying and dispersing agent contains not more than 1 part by weight of a polyoxyethylene-based nonionic surfactant per 100 parts by weight of vinyl acetate units in the vinyl acetate-ethylene copolymer. Method for producing emulsion adhesive with excellent properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4278112A JP2657600B2 (en) | 1992-09-21 | 1992-09-21 | Emulsion adhesive excellent in initial adhesiveness and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4278112A JP2657600B2 (en) | 1992-09-21 | 1992-09-21 | Emulsion adhesive excellent in initial adhesiveness and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06100751A JPH06100751A (en) | 1994-04-12 |
| JP2657600B2 true JP2657600B2 (en) | 1997-09-24 |
Family
ID=17592795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4278112A Expired - Fee Related JP2657600B2 (en) | 1992-09-21 | 1992-09-21 | Emulsion adhesive excellent in initial adhesiveness and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2657600B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105694618A (en) * | 2016-03-04 | 2016-06-22 | 芜湖市金宇石化设备有限公司 | Treating agent for coating crane tube |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3959150B2 (en) * | 1997-04-02 | 2007-08-15 | 株式会社沖データ | Heater control method for facsimile machine |
| DE69810017T2 (en) | 1997-07-03 | 2003-09-25 | Sumitomo Chemical Co., Ltd. | Process for the preparation of an aqueous emulsion |
| JP2000053711A (en) * | 1998-08-11 | 2000-02-22 | Clariant Polymer Kk | Re-dispersible emulsion powder and its production |
| DE102005054904A1 (en) * | 2005-11-17 | 2007-05-24 | Wacker Polymer Systems Gmbh & Co. Kg | Process for the preparation of polyvinyl alcohol-stabilized latexes |
| CN115368864B (en) * | 2022-06-08 | 2023-08-25 | 有行鲨鱼（上海）科技股份有限公司 | Water-based jigsaw for cork and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5222760B2 (en) * | 1973-06-13 | 1977-06-20 | ||
| JPH0655874B2 (en) * | 1989-02-28 | 1994-07-27 | 住友化学工業株式会社 | Vinyl acetate-ethylene copolymer emulsion and method for producing the same |
-
1992
- 1992-09-21 JP JP4278112A patent/JP2657600B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694618A (en) * | 2016-03-04 | 2016-06-22 | 芜湖市金宇石化设备有限公司 | Treating agent for coating crane tube |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06100751A (en) | 1994-04-12 |
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